Naphtha reforming catalyst and preparation method thereof

Patent metadata

Field	Value
Publication number	US-9623403-B2
Application number	US-201514831526-A
Country	US
Kind code	B2
Filing date	Aug 20, 2015
Priority date	Aug 25, 2014
Publication date	Apr 18, 2017
Grant date	Apr 18, 2017

Abstract

A naphtha reforming catalyst, comprising an alumina support and following components with the content calculated on the basis of the support: VIII group metal 0.1-2.0% by weight, VIIB group metal 0.1-3.0% by weight, sulfate ion 0.45-3.0% by weight, and halogen 0.5-3.0% by weight. The catalyst is used in a naphtha reforming reaction without presulfurization and has a high aromatization activity and a selectivity.

First claim

We claim:

1. A naphtha reforming catalyst, comprising: a sulfate ion-containing alumina support, and a VIII group metal of 0.1-2.0% by weight, a VIIB group metal of 0.1-3.0% by weight, and a halogen of 0.5-3.0% by weight supported on the alumina support,
wherein the alumina support comprises sulfate ions of 0.45-3.0% by weight and a sodium content of 0.008-0.03% by weight,
wherein the weight percentages are calculated based on a weight of the alumina support, and
wherein, in said catalyst, a ratio of a pore volume of pores with a pore radius between 3 nm and 10 nm to a total pore volume is from 60% to 85%, a ratio of a pore volume of pores with a pore radius smaller than 3 nm to the total pore volume is not more than 36%, and a ratio of a pore volume of pores with a pore radius larger than 10 nm to the total pore volume is more than 2%.

2. The catalyst according to claim 1 , characterized in that said catalyst further comprises 0.01% to 3.0% by weight, based on the weight of the alumina support, of one or more rare earth elements selected from the group consisting of ytterbium, yttrium, europium and cerium.

3. The catalyst according to claim 2 , characterized in that said VIII group metal is selected from the group consisting of platinum, ruthenium, rhodium and iridium; the VIIB group metal is rhenium; and the halogen is chlorine.

4. The catalyst according to claim 2 , characterized in that said catalyst has content of sulfate ions of 0.45-2.0% by weight.

5. The catalyst according to claim 2 , characterized in that a specific surface area of said catalyst is from 180 m 2 /g to 300 m 2 /g.

6. The catalyst according to claim 2 , characterized in that said sulfate ion-containing alumina support has content of sodium of from 0.01% to 0.03% by weight.

7. The catalyst according to claim 2 , characterized in that in said catalyst, the ratio of the pore volume of the pores with a pore radius between 3 nm and 10 nm to the total pore volume is from 70% to 85%; the ratio of the pore volume of the pores with a pore radius smaller than 3 nm to the total pore volume is not more than 25%; and the ratio of the pore volume of the pores with a pore radius larger than 10 nm to the total pore volume is from 5% to 10%.

8. The catalyst according to claim 1 , characterized in that said VIII group metal is selected from the group consisting of platinum, ruthenium, rhodium and iridium; the VIIB group metal is rhenium; and the halogen is chlorine.

9. The catalyst according to claim 1 , characterized in that said catalyst comprises sulfate ions of 0.45-2.0% by weight.

10. The catalyst according to claim 1 , characterized in that a specific surface area of said catalyst is from 180 m 2 /g to 300 m 2 /g.

11. The catalyst according to claim 1 , characterized in that said sulfate ion-containing alumina support comprises sodium of from 0.01% to 0.03% by weight.

12. The catalyst according to claim 1 , characterized in that in said catalyst, the ratio of the pore volume of the pores with a pore radius between 3 nm and 10 nm to the total pore volume is from 70% to 85%, the ratio of the pore volume of the pores with a pore radius smaller than 3 nm to the total pore volume is not more than 25%, and the ratio of the pore volume of the pores with a pore radius larger than 10 nm to the total pore volume is from 5% to 10%.

13. A method for preparation of the catalyst according to claim 1 , comprising the following steps:
(1) mixing sodium aluminate and aluminum sulfate in a molar ratio of 1 to 10:1, controlling pH value of a solution to between 7 and 11 to obtain a precipitation by a two-stage precipitation method, wherein in the first stage, the pH value of the system is adjusted between 7.3 and 8.5 for precipitation for 10 to 50 minutes, and in the second stage, the pH value of the system is adjusted between 8.6 and 10.0 followed by aging, the aging being at a temperature in the range of 60° C. to 150° C., and the solid substance obtained subjecting to water-washing and drying to produce a pseudo-boehmite powder containing sulfate ions, wherein the sulfate ions is 0.45% to 3.0% by weight calculated based on a weight of alumina;
(2) adding an acidic solution in the pseudo-boehmite powder produced in step (1), for kneading and extruding, then drying and calcinating to produce the alumina support containing sulfate ions;
(3) optionally subjecting the alumina support produced in step (2) to a hydro-thermal treatment at a temperature in the range of 450° C. to 850° C.;
(4) impregnating the alumina support produced in step (2) or the alumina support produced in in step (3) with an aqueous solution comprising the VIII group metal, the VIIB group metal and the halogen, then drying and calcinating the impregnated alumina support.

14. The method according to claim 13 , characterized in that the method comprises said hydro-thermal treatment in step (3).

15. The method according to claim 13 , characterized in that the impregnation solution in step (4) further comprises ytterbium, yttrium, europium and/or cerium.

16. The method according to claim 15 , characterized in that ytterbium, yttrium, europium and/or cerium in the impregnation solution are derived from a nitrate and/or a chloride thereof.

17. The method according to claim 13 , characterized in that the hydro-thermal treatment in step (3) is carried out in humidified air or in steam for 2 hours to 30 hours.

18. The method according to claim 13 , characterized in that the product after the reaction in step (1) is aged for 2 hours to 48 hours.

19. The method according to claim 13 , characterized in that in the impregnation solution of step (4), the VIII group metal is derived from chloroplatinic acid, tetraaminoplatinum dichloride, ammonium chloroplatinate, platinum trichloride, platinum tetrachloride hydrate, dicarbonyl platinum dichloride, dinitrodiaminoplatinum and/or sodium tetranitropalatinate.

20. The method according to claim 13 , characterized in that in the impregnation solution of step (4), the VIIB group metal is derived from perrhenic acid and/or ammonium perrhenate, and the halogen is introduced via HCl.

Assignees

• China Petroleum & Chem Corp
• Res Inst Petroleum Processing Sinopec

Inventors

• Zhang Daqing
• Zang Gaoshan
• Zhang Yuhong
• Wang Jiaxin
• Wang Tao

Classifications

• B01J37/0018

  Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat) · CPC title

• B01J37/0201

  Impregnation · CPC title

• B01J23/63

  with rare earths or actinides · CPC title

• B01J27/053

  Sulfates · CPC title

• B01J23/6567

  Rhenium · CPC title